Sulfur containing nanoporous materials, nanoparticles, methods and applications

ABSTRACT

Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or “bulk” shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.

CROSS-REFERENCE TO RELATED APPLICATION

This application is related to, and derives priority from, U.S.Provisional Patent Application Ser. No. 61/411,645, filed 9 Nov. 2010and titled Nanocomposite for Lithium Battery—Apparatus, Method andApplications, the content of which is incorporated herein fully byreference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with government support under contract no.DE-SC0001086awarded by the Department of Energy. The government hascertain rights in the invention.

BACKGROUND

Field of the Invention

Embodiments relate generally to sulfur containing nanoporous materialsand nanoparticles. More particularly, embodiments relate to sulfurcontaining nanoporous materials, nanoparticles, methods andapplications.

Description of the Related Art

Among cathode materials for secondary lithium batteries, elementalsulfur has a very high theoretical capacity, 1672 mAhg⁻¹ againstlithium, which is considerably greater than that of many commerciallyused transition metal phosphates and transition metal oxides. Inaddition, elemental sulfur also provides several other advantages as acathode material for a secondary lithium battery, including inparticular a low cost and a widespread availability. Sulfur hasconsequently been studied extensively as a cathode material forsecondary lithium batteries and is considered a promising candidate fora cathode material for secondary lithium batteries that may be used inelectric and hybrid electric vehicles.

Despite this promise, implementation of Li—S secondary battery systemsfor high power applications has been problematic for various reasons.Thus, desirable are methods and materials that provide an opportunity tomore fully realize the advantages of sulfur as a cathode material withina Li—S secondary battery system.

SUMMARY

Embodiments provide sulfur containing nanoporous materials andnanoparticles, and methods for fabricating the sulfur containingnanoporous materials and nanoparticles. The sulfur containing nanoporousmaterials and nanoparticles in accordance with the embodiments may beused as active materials (or a source of active materials) within acathode within a lithium ion battery to provide a lithium-sulfursecondary battery system with enhanced performance and properties. Inaddition to the sulfur containing nanoporous materials and nanoparticlesand methods for fabricating the sulfur containing nanoporous materialsand nanoparticles in accordance with the embodiments, the resultingcathodes and the resulting lithium ion batteries that incorporate thesulfur containing nanoparticles are also included within theembodiments.

A nanoparticle in accordance with one particular embodiment provides asulfur material infused carbon material shape nanoparticle (i.e.,typically a hollow sphere) that may be fabricated using a pyrolysis of acarbon precursor material upon a template nanoparticle, followed bydissolution of the template nanoparticle and infusion of the remaininghollow carbon material shape with a sulfur material. These particularnanoparticles provide when incorporated as an active material into acathode for use within a lithium-sulfur electrochemical cell a cyclicvoltammogram that shows a stable two step oxidation process and a stabletwo step reduction process (i.e., the stable two step oxidation processand the stable two step reduction process are intended to exhibit noappreciable voltage shifts (i.e., less than about 0.2 volts) or peakheight variation (i.e., less than about 20% variation) with repetitivebattery charge cycling and discharge cycling of up to at least about 100cycles.

A nanoporous material in accordance with the foregoing particularnanoparticle related embodiment may also include a larger “bulk” (i.e.,at least millimeter sized, and generally even at least centimeter sizedand larger than centimeter sized) nanoporous carbon material shape thatis similarly infused with sulfur. This larger “bulk” sulfur materialinfused nanoporous carbon material shape may be ground intonanoparticles that provide when incorporated as an active material intoa cathode for use within a lithium-sulfur electrochemical cell thecyclic voltammogram that shows the stable two step oxidation process andthe stable two step reduction process, as above. Thus, this particularfirst embodiment contemplates that properly sized carbon material shapenanoparticles may be first formed and then infused with a desirablesulfur material. This particular first embodiment also contemplates thata larger “bulk” nanoporous carbon material shape may first be infusedwith the desirable sulfur material and then ground into the desired endproduct sulfur infused carbon material shape nanoparticles.

Another particular embodiment provides a metal oxide core nanoparticleto which is bonded a vulcanized polymultiene polymer material and ionconducting polymer material shell. When incorporated as an activematerial into a cathode for use within a lithium-sulfur electrochemicalcell, these particular nanoparticles also show enhanced electrochemicalperformance within the context of charge and discharge cycling of thelithium-sulfur electrochemical cell.

A particular nanoparticle in accordance with the embodiments includes acarbon material support. The particular nanoparticle also includes asulfur material supported on the carbon material support. A cyclicvoltammogram of a lithium-sulfur cell that includes the nanoparticle asan active material within a cathode shows a stable reduction peak atabout 2.4 volts.

A particular nanoporous material in accordance with the embodimentsincludes a bulk carbon material support. This particular nanoporousmaterial in accordance with the embodiments also includes a sulfurmaterial supported on the bulk carbon material support. A cyclicvoltammogram of a lithium-sulfur cell that includes a nanoparticlederived from the nanoporous material within a cathode shows a stablereduction peak at about 2.4 volts.

A particular method for fabricating the particular foregoingnanoparticle in accordance with the embodiments includes infusing at atemperature of at least about 450 degrees Celsius and a vapor pressureof at least about 2 atmospheres into a porous carbon material support asulfur material source to provide a sulfur infused porous carbonmaterial support.

Another particular method for fabricating a nanoparticle in accordancewith the embodiments includes infusing at a temperature at least about450 degrees Celsius and a pressure at least about 2 atmospheres a bulkporous carbon material support with a sulfur material source to providea sulfur infused bulk porous carbon material support. This otherparticular method also includes grinding the sulfur infused bulk porouscarbon material support to form the nanoparticle.

Another particular nanoparticle in accordance with the embodimentsincludes a core comprising a metal oxide material. This other particularnanoparticle also includes a shell layer located encapsulating the coreand comprising a sulfur cross-linked polymultiene polymer materialcoupled with an ion conducting polymer material.

Another method for fabricating this other particular nanoparticle inaccordance with the embodiments includes forming an organofunctionalmetal oxide core. This other method also includes reacting theorganofunctional metal oxide core with one of a multifunctionalpolymultiene polymer material and a multifunctional ion conductingpolymer material to form a partially sheathed metal oxide core. Thisother method also includes reacting the partially sheathed metal oxidecore with a complementary one of a functional polymultiene polymermaterial and a functional ion conducting polymer material to form apolymultiene polymer material and ion conducting polymer material shellbonded to the organofunctional metal oxide core. This other method alsoincludes vulcanizing the polymultiene polymer material with a sulfurmaterial.

BRIEF DESCRIPTION OF THE DRAWINGS

The objects, features and advantages of the embodiments are understoodwithin the context of the Detailed Description of the Embodiments, asset forth below. The Detailed Description of the Embodiments isunderstood within the context of the accompanying drawings, that form amaterial part of this disclosure, wherein.

FIG. 1 shows transmission electron microscopy images of high surfacearea silica template nanoparticles (FIG. 1a ) and carbon coated highsurface area silica template nanoparticles (FIG. 1b ) in accordance witha first embodiment.

FIG. 2 shows transmission electron microscopy images of high surfacearea hollow carbon spheres (FIG. 2a ), sulfur infused high surface areahollow carbon spheres (FIG. 2b ) and a graph of Counts versus Energy foran energy dispersive x-ray (EDX) analysis of the sulfur infused highsurface area hollow carbon spheres (FIG. 2c ) in accordance with thefirst embodiment.

FIG. 3 shows a nitrogen sorption isotherm (FIG. 3a ) and pore sizedistribution graph (FIG. 3b ) of the high surface area hollow carbonspheres in accordance with the first embodiment.

FIG. 4 shows an image of a custom fabricated segmented glass tube usedfor vapor phase infusion of sulfur into the high surface area hollowcarbon spheres in accordance with the first embodiment.

FIG. 5 shows a thermal gravimetric analysis (TGA) graph for sulfurinfused high surface area hollow carbon spheres in accordance with thefirst embodiment.

FIG. 6 shows an x-ray diffraction (XRD) analysis graph for high surfacearea hollow carbon spheres before and after sulfur infusion inaccordance with the first embodiment.

FIG. 7 shows an X-ray Diffraction Graphite Calibration Curve forestimating graphite content of the high surface area hollow carbonspheres in accordance with the first embodiment.

FIG. 8 shows a Raman spectrum of the high surface area hollow carbonspheres in accordance with the first embodiment.

FIG. 9 shows a Raman Graphite Calibration Curve for estimating graphitecontent of the high surface area hollow carbon spheres in accordancewith the first embodiment.

FIG. 10 shows a cyclic voltammogram (FIG. 10a ) and voltage versuscapacity profiles (FIG. 10b ) for electrodes fabricated incorporatingsulfur infused high surface area hollow carbon spheres in accordancewith the first embodiment.

FIG. 11 shows Voltage versus Capacity (FIG. 11a ) and Capacity versusCycle Number (FIG. 11b ) for pristine sulfur cells, as well as Capacityversus Cycle Number (FIG. 11c ) based upon sulfur mass or sulfur/carbonmass, for comparison within the context of the first embodiment.

FIG. 12 shows Voltage versus Capacity for a lithium ion battery cellwhile varying a charge rate for a cathode that includes sulfur infusedhigh surface area hollow carbon spheres in accordance with the firstembodiment.

FIG. 13 shows graphs of Capacity versus Cycle Number yielding cycle life(FIG. 13a ) and rate capability (FIG. 13b ) for electrochemical cellsfabricated using electrodes incorporating the sulfur infused highsurface area hollow carbon spheres in accordance with the firstembodiment.

FIG. 14 shows a plurality of graphs and images illustrating extension ofthe sulfur infused high surface area hollow carbon spheres in accordancewith the first embodiment to provide additional sulfur infused carbonnanoparticle electrodes that may be incorporated into lithium ionbatteries.

FIG. 15 shows a diagram illustrating a generalized synthetic scheme forsynthesizing a plurality of sulfur sequestered nanoparticle materials inaccordance with a second embodiment.

FIG. 16 shows titration data for forming a sulfur sequesterednanoparticle material in accordance with the second embodiment.

FIG. 17 shows scanning electron microscopy (SEM) images of sulfursequestered nanoparticle materials in accordance with the secondembodiment.

FIG. 18 shows thermal gravimetric analysis (TGA) spectra of sulfursequestered nanoparticle materials in accordance with the secondembodiment.

FIG. 19 shows a Modulus versus Strain diagram for sulfur sequesterednanoparticle materials in accordance with the second embodiment.

FIG. 20 show differential scanning calorimetry (DSC) spectra for sulfursequestered nanoparticle materials in accordance with the secondembodiment.

FIG. 21 shows a cyclic performance graph illustrating capacity versuscycle number for lithium ion batteries incorporating the sulfursequestered nanoparticle materials in accordance with the secondembodiment.

FIG. 22 shows a bulk porous carbon shape (FIG. 22a ) and a sulfurinfused high surface area bulk porous carbon shape (FIG. 22b ) fromwhich may be fabricated a sulfur infused high surface area nanoparticlematerial in accordance with an extension of the first embodiment.

FIG. 23 shows a transmission electron microscopy (TEM) image of a sulfurinfused high surface area nanoparticle material in accordance with FIG.14a , but including a dimensional scale.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Embodiments provide a plurality of sulfur containing nanoporousmaterials and nanoparticles that may be used within a cathode within alithium ion battery, as well as a corresponding plurality of methodsthat may be used for fabricating the plurality of sulfur containingnanoporous materials and nanoparticles that may be used within thecathode within the lithium ion battery. The cathode and the lithium ionbattery that use the sulfur containing nanoparticles are also includedwithin the embodiments.

In accordance with one particular embodiment, the sulfur containingnanoporous materials and nanoparticles comprise a sulfur materialinfused carbon material shape nanoparticle. (i.e., such as but notlimited to a sphere or other hollow capsule shape, or alternatively anon-hollow shape). The sulfur material (i.e., typically elementalsulfur) is infused into the carbon material shape to provide a sulfurinfused carbon nanoporous material shape or nanoparticle at atemperature at least about 450 degrees Celsius and at comparatively highpressure of at least about 2 atmospheres.

In accordance with another particular embodiment, the sulfur containingnanoparticles comprise a metal oxide core to which is bonded a shellthat comprises a vulcanized polymultiene polymer material (i.e.,typically but not limited to a polybutadiene polymer material) and ionconducting polymer material (i.e., typically but not limited to apolyethyleneglycol polymer material). This other particular sulfurcontaining nanoparticle typically comprises: (1) a metal oxide materialcontent from about 2 to about 20 weight percent; (2) a polymultienepolymer material content from about 10 to about 40 weight percent; (3)an ion conducting polymer material content from about 2 to about 5weight percent; and (4) a sulfur material content from about 2 to about80 weight percent.

Each of the foregoing two particular embodiments is describedindividually in greater detail below.

I. Sulfur Containing Nanoparticle Comprising Sulfur Material InfusedHollow Carbon Material Shape Nanoparticles

This particular first embodiment includes a facile and scalable methodfor synthesizing mesoporous hollow carbon material shapes (i.e.,capsules such as but not limited to spheres) that encapsulate andsequester a sulfur material (and in particular an elemental sulfurmaterial) in their interiors, and also within their porous shells. Theinterior void space, the mesoporous shell structure, a chemical make-upof the shell and a methodology used to infuse sulfur into the carbonmaterial shapes are designed with four specific goals underconsideration. The four specific goals include: (i) an intent tomaximize an amount of sulfur material sequestered by the carbonmaterials capsules; (ii) an intent to minimize lithium polysulfidedissolution and shuttling in an electrolyte; (iii) an intent to preservefast transport of lithium ions to the sequestered sulfur by ensuringgood electrolyte penetration; and (iv) an intent to facilitate goodtransport of electrons from the poorly conducting sulfur, undercircumstances where the hollow carbon material shapes infused with thesulfur material are incorporated into a cathode material in a Li—Ssecondary battery. As discussed in greater detail below, the as preparedS@C carbon-sulfur nanocomposite shapes were found to manifest promisingelectrochemical behavior upon extended cycling for 100 cycles at 850mA/g (0.5 C), consistent with desirable goals in designing the hollowcarbon material shapes. The electrochemical stability of the S@Ccomposites was confirmed using extended scan cyclic voltammetrymeasurements.

In a first step of the synthesis of the S@C composites, carbon sphereswere fabricated by pyrolysis of a low-cost carbon precursor material(e.g., pitch material, although as discussed further below other carbonprecursor materials are not precluded) uniformly deposited onto and intothe pores of porous metal oxide template nanoparticles (see, e.g., FIG.1a for a TEM image of silica template nanoparticles in accordance withthe first embodiment and FIG. 1b for a TEM image of carbon coated silicatemplate nanoparticles in accordance with the first embodiment).Subsequent dissolution of the silica template nanoparticle supportsyielded well-defined hollow carbon shapes that are illustrated in theTEM image of FIG. 2a . By manipulating the metal oxide templatenanoparticle size and porosity, hollow carbon spheres with high specificsurface area of 648 m²g⁻¹ (see, e.g., FIG. 3a ; and generally in aspecific surface area range from about 100 to about 1500 m²g⁻¹), 1 nmaverage pore diameter (see, e.g., FIG. 3b ; and generally in a porediameter range from about 0.5 to about 20 nm), and large internal voidspace (see, e.g., FIG. 2a ) were facilely fabricated. In a final step ofthe synthesis, advantage was taken of the relatively low sublimationtemperature of sulfur to infuse gaseous sulfur at high pressure into themesoporous hollow carbon sphere shape supports present in onecompartment of a closed, dual-compartment segmented tube, as isillustrated in FIG. 4. This methodology facilitates fast, efficient, andcontrolled infusion of elemental sulfur at high pressure (i.e., at leastabout 2 atmospheres, more preferably at least about 5 atmospheres andyet more preferably at least about 8 atmospheres, but more specificallyin a range from about 2, 5 or 8 atmospheres to about 20 atmospheres)into the host porous carbon shape structure and yields carbon-sulfurparticles with high tap density of at least about 0.82 gcm⁻³. Thisparticular methodology also contemplates use of an inert gas (i.e., suchas but not limited to helium, neon or argon) which is heated inconjunction with elemental sulfur to assist in providing the foregoingelevated pressure in conjunction with sulfur infusion. As is illustratedin FIG. 5, thermal gravimetric analysis shows that approximately 35%sulfur can be incorporated in the particles in a single pass, and thatby three passes (i.e. repeat exposures of the hollow carbon shapes tosulfur vapor), nearly 70% of the mass of the porous and hollow carbonshapes is comprised of infused sulfur.

FIG. 2a and FIG. 2b show a transmission electron microscopy (TEM) imageof typical hollow carbon material shape spheres before and after sulfurmaterial infusion. The high surface area and relatively large mesoporesizes of the hollow carbon material sphere shapes are attractive sincethey are anticipated to allow an electrolyte and Li ions produced from aLi—S redox reaction to penetrate the hollow carbon material sphereshapes. While creating occasional ruptures in the walls of the hollowcarbon materials sphere shapes (e.g. see bottom most hollow carbonmaterial sphere shape in FIG. 2b ), a pressure built-up in the Pyrextube used for sulfur infusion is as described above integral forfacilitating complete incorporation of the sulfur into the hollow carbonmaterial sphere shape host in a fashion that provides desirableelectrochemical properties. Elemental composition of the S@Cnanocomposites analyzed by energy-dispersive x-ray (EDX) microanalysisis shown in FIG. 2(c). EDX spectra collected from different locationswithin the mesoporous S@C material also indicate the presence of sulfurmaterials throughout the porous hollow carbon material sphere shapes.

Elemental sulfur generally exists in a very stable orthorhombiccrystalline structure. The absence of characteristic peaks forcrystalline sulfur in the x-ray diffraction spectrum of FIG. 6 indicatesa very low degree of sulfur crystallization in the S@C nanocomposite inaccordance with this first embodiment. This suggests that the sublimedand infused sulfur is amorphous or that the sulfur particles trapped inthe finest pores of the mesoporous hollow carbon shape spheres areunable to crystallize. XRD indicates, however, that the carbon materialpossesses some crystalline order, which is indicative of graphiticcharacter for the materials considered here. The relative peak areas canbe analyzed to estimate the degree of graphitization or the orientationof graphite planes. This analysis, as illustrated in FIG. 7, indicatesthat more than 38% of the material is graphitic carbon. The relativeintensity of the D- and G-Raman scattering peaks at 1350 and ˜1580 cm⁻¹,respectively provides a well-known alternative method for identifyingcarbon, as well as for assessing its graphitic content. The presence ofboth the D- and G-Raman bands in the carbon shape spheres is confirmedin the Raman spectrum shown in FIG. 8. The graphitic content can beestimated to be around 16%, and the difference between the two estimatesmay be attributed to a higher uncertainty of the Raman calibration curveFIG. 9. Because the electrical conductivity of graphitic carbon issubstantially higher than of amorphous carbon, even partiallygraphitized carbon shape nanoparticles are attractive insofar as theyfacilitate transport of electrons from the poorly conducting infusedsulfur, thus aiding electrochemical stability of the S@C nanocompositehollow shapes even at high discharge rates.

A cyclic voltammogram (CV) of an electrode incorporating the S@Cnanocomposite is shown in FIG. 10a . The pair of sharp redox peaksindicates that during charge/discharge the electrochemical reduction andoxidation of sulfur occurs in two stages. The first peak at 2.4 V(designated as II) involves the reduction of elemental sulfur to lithiumpolysulfide (Li₂S_(n), 4≦n≦8). The second peak at 2.0 V (designated asIII) involves the reduction of sulfur in lithium polysulfide to Li₂S₂and eventually to Li₂S. The oxidation process in the Li—S cell alsooccurs in two stages. The oxidation peak at 2.35 V (designated as II′)is associated with the formation of Li₂S_(n) (n>2). This processcontinues until lithium polysulfide is completely consumed and elementalsulfur produced at 2.45 V (designated as III′). Significantly, nochanges in the CV peak positions or peak current (inset in FIG. 10a )are observed, even after 60 scans, confirming the electrochemicalstability of the S@C composites and indicating that the porous carbonstructure is quite effective in preventing the loss of sulfur into theelectrolyte and in maintaining high utilization of the active sulfur inthe redox reactions.

FIG. 10b shows typical discharge/charge voltage profiles for anelectrode incorporating the S@C nanocomposite. It is immediatelyapparent from FIG. 10b that the discharge/charge voltage plateaus,marked as II, IV, II′ and IV′, exactly resemble the redox peaks observedin the CV scans, which are also marked as II, IV, II′ and IV′. Theoxidation peak at 2.45 V observed in the CV experiments has not beenpreviously reported, though the corresponding charge plateau andreaction are well documented in the literature; its presence here nicelycorroborates the reversibility of the electrochemical reactionsoccurring in the S@C nanocomposite. As shown in FIG. 10b , the asprepared S@C nanocomposites manifest an initial specific dischargecapacity of 1071 mAhg⁻¹ and maintains a reversible capacity of 974mAhg⁻¹ (at a rate of 0.5 C) with 91% capacity retention after 100cycles. For completeness, FIG. 11c reports the corresponding specificcapacities based on the combined mass of the S@C composite. It isevident from FIG. 11c that by either measure the specific capacityvalues are attractive from the point of view of intended batteryapplications. Additionally, no changes in the voltage plateaus are seenafter 100 cycles, indicating that the electrochemical processes aresubstantially unchanged during extended cycling of the cell, which isalso desirable for battery applications.

FIG. 12 reports the voltage profile for the materials, which show thesame pattern of discharge and charge plateaus even at very high currentrates. The rate capability and cycle life behavior of the S@Cnanocomposite are considered in greater detail in FIG. 13a and FIG. 13b. Specifically, FIG. 13a shows that there is some capacity fade uponextended cycling, but reveals no evidence of the dramatic capacityreduction characteristic of Li—S cells upon extended cycling. Since thereversible Li—S₈ redox reaction occurs via the non-topotacticassimilation process, the volume expansion due to sulfur incorporatedinto the host carbon structure, following subsequent discharge/chargereaction is anticipated to be small. On the other hand, thecharge-discharge behavior of pristine sulfur shown in FIG. 11a and FIG.11b , display a notable decrease in discharge capacity and an imperfectcharging characteristic for a shuttle mechanism.

Once the shuttle mechanism is started, as can be seen in FIG. 11a , thecharging behavior at about 2.4 V continues without overcharging,resulting in a decrease in charge efficiency at the end of the chargeand the discharge capacity is reduced. The columbic efficiency of theS@C nanocomposite in the first cycle is computed to be 96% in comparisonto 94% after 100 cycles, indicating reliable stability. In contrast, thecolumbic efficiency of pristine sulfur (see FIG. 11b ) in the firstcycle is calculated as 77%, which reduces to 31% by the end of 8 cycles.The pristine material subsequently displays the well-known continuouscharging process due to an increased content of polysulfides in theelectrolyte. The rate capability behavior of the S@C nanocomposite athigher rates is shown in FIG. 13b . At the maximum discharge ratestudied, 3 C (5.1 A/g), the material is seen to deliver 450 mAhg⁻¹,which is an unprecedented result for a Li—S secondary battery cycled atthis high rate. The stability of the cathode material is also evidencedby the recovery of a capacity of 891 mAhg⁻¹ at 0.5 C rate followingcharging at the rather high rate (for a Li—S cell) of 3 C (FIG. 13b ).

The excellent overall electrochemical behavior of the as prepared S@Ccomposites can be attributed to multiple, possibly synergistic factorsthat stem from their design. First, the mesoporous high surface areacarbon host facilitates high levels of sulfur deposition onto, as wellas into, the adsorbing carbon framework. Based on the exceptionalelectrochemical stability of the materials it is considered thatconfinement of sulfur in the pores and interior void space of thisframework minimize loss of lithium polysulfides to the electrolyte anddisfavors shuttling. Second, the partially graphitic character of thecarbon framework is believed to provide mechanical stability to thedeposited sulfur film and also allows effective transport of electronsfrom/to the poorly conducting active material. It is believed that thislatter feature is responsible for the electrochemical stability of thematerial at high current densities; it is expected to improve as thegraphitic content of the carbon shapes increase. Finally, the pores inthe framework are large-enough to allow ready access by electrolyte andpreserve fast transport of Li⁺ ions to the active material.

In summary, a facile, scalable procedure is described above forsynthesizing S@C nanocomposites based on mesoporous hollow carbonshapes. The method uses a template-based approach for synthesizinghollow carbon shaped particles with desirable features andhigh-pressure, vapor phase infusion of elemental sulfur into the poresand center of the carbon shapes to produce fast, efficient uptake ofelemental sulfur. When evaluated as the cathode material in a Li—Ssecondary battery, the as prepared S@C nanocomposites displayoutstanding electrochemical features at both low and high currentdensities. The materials described herein are among the first to offerextended cycle life and high charge rate capability in a secondary Li—Sbattery. These observations are attributed to sequestration of elementalsulfur in the carbon shapes and to its favorable effect in limitingpolysulfide shuttling, as well as to enhanced electron transport fromthe poorly conducting sulfur made possible by its close contact with thecarbon framework.

A. Experimental Details

Mesoporous hollow carbon shape spheres were prepared by a hard templateapproach. In a typical synthesis, highly porous silica templates (2 g)synthesized by a conventional method were suspended in 50 ml ofN-Methyl-2-pyrrolidone (NMP, Aldrich) solution containing 1.05 g ofpetroleum pitch (Carbonix, South Korea). The suspension was sonicatedfor 20 minutes and transferred to a rotavap for distillation andcomplete solvent removal at 110° C. The petroleum pitch coated silicaparticles were then vacuum dried at 110° C. for 12 h; calcination at1300° C. for 12 h under argon flow followed. The carbon coated silicaparticles obtained in this stage were treated with HF (Aldrich) to etchaway the silica template and then dried after subsequent washes withwater and ethanol. Sulfur incorporation was performed using ahigh-pressure, vapor phase infusion method.

The S@C cathode slurry was created by mixing 92.5% of the composite (70%sulfur and 30% carbon hollow spheres) and 7.5% of PVDF binder in a NMPsolvent dispersant. Positive electrodes were produced by coating theslurry on aluminum foil and drying at 120° C. for 12 h. The resultingslurry-coated aluminum foil was roll-pressed and the electrode wasreduced to the required dimensions with a punching machine. Theelectrode thickness of the entire prepared electrodes was similar (˜80μm) after 85% reduction of the original thickness through the rollpress. The same procedure was followed to prepare pristine sulfurcathode, except that the cathode slurry was made of 80% of elementalsulfur, 10% of Super P conducting carbon and 10% PVDF binder in NMPdispersant. Preliminary cell tests were conducted on 2032 coin-typecells, which were fabricated in an argon-filled glove box using lithiummetal as the counter electrode and a micro porous polyethyleneseparator. The electrolyte solution was 1 M lithium bis(trifluoromethane sulfone) imide (LiTFSI) in tetraglyme. Cyclicvoltammetry studies were performed on a Solartron's Cell Test modelpotentiostat. Electrochemical charge discharge analysis, under thepotential window 3.1 to 1.7 V, was carried out using Maccor cycle lifetester.

B. Considerations Related to Sulfur Material Infused Carbon MaterialNanocomposites from Other Sources

The elevated pressure vapor infusion approach used to create themesoporous, hollow carbon-sulfur composite materials from petroleumpitch can be used to produce high-power sulfur cathodes using othercarbon sources that are nominally bulk sources (e.g. coal, high-sulfurcoal, charcoal, and organic polymer aerogels). FIG. 14, FIG. 22 and FIG.23 for example, summarize results obtained using a commercial carbonprecursor obtained by pyrolizing a resorcional-formaldehyde polymeraerogel in an inert atmosphere environment. The material was provided asa gift by American Aerogel and is being marketed for insulationproducts. The carbon materials were first activated at temperaturesranging from 1000-1250° C. in an inert (argon) atmosphere. FIG. 22Ashows a transmission electron microscopy image of the carbon aerogelmaterial illustrating that following carbonization it is a formless mass(i.e., the material shows none of the nanostructuring of the carbonshape spheres described above). FIG. 22B shows a transmission electronmicroscopy image of the carbon aerogel after sulfur infusion inaccordance with the method described above for sulfur infusion intohollow carbon material shape spheres.

FIG. 23 and FIG. 14a show nanoparticles that are formed incident togrinding of the sulfur infused carbon material formless mass of FIG.22B. These resulting sulfur infused carbon nanoparticles were of sizesimilar to the hollow carbon nanoparticle spheres described above, andthey were fabricated into cathode electrodes using similar methods andmaterials.

FIG. 14B to FIG. 14E show, that this additional sulfur infusednanoparticle carbon material shares multiple features with the hollowcarbon shape spheres described above.

Specifically, FIG. 14B and FIG. 14C are results from BET porosimetrymeasurements, which show that the material has a high specific surfacearea (257 m2/g) and small average pore size (3.8 nm). FIG. 14D and FIG.14E are the Raman and wide-angle x-ray diffraction spectra for thematerial. The presence of the G-band in the Raman spectrum and thedistinct peaks in the x-ray diffraction spectra, imply that the materialis crystalline. The upper plot in FIG. 14E is the x-ray diffractionspectrum of the material after infusion of sulfur using the same vaporphase sulfur infusion method that was used for the hollow carbon shapespheres. An energy dispersive x-ray (EDX) spectra of the material aftersulfur infusion is shown in FIG. 14F, which shows that it is comprisedof (i.e., consists of) carbon and sulfur only. The upper plot in FIG.14E therefore implies that the adsorbed sulfur is amorphous.Quantitative analysis of the Raman and XRD data imply that at least 10%of the carbon is graphitic.

Thermal gravimetric analysis of the S/C composite indicates that 59% ofthe mass of the material is sulfur. As illustrated in FIG. 14G and FIG.14H, cyclic voltammetry (in particular) and related electrochemicalmeasurements show that the S/C composite obtained using the AmericanAerogel material is electrochemically stable and for all practicalpurposes identical to the S/C composites obtained using mesoporous,hollow carbon shape spheres as described above. FIG. 14I shows theenergy storage capacity at a charge rate of 0.5 C achieved when thematerial is used as the cathode in a coin cell employing lithium metalas anode. The data of FIG. 14I show that the material deliverscapacities over 600 mAh/g after more than 600 charge-discharge cycles.The specific capacity and capacity retention of the S/C compositecathodes are modestly lower than those observed for the carbon spheres,but this difference may presumably be readily removed by increasing thelevel of sulfur infusion (e.g. using multiple passes).

S/C composite particles can be created using a variety of other carbonsources (polyacrylonitrile (PAN), polysaccharides (e.g. glucose), citricacid, gallic acid, cynnamic acid and polymeric cores (e.g. polystyrene,polymethylmethacrylate). Following high-temperature pyrolysis, theelevated pressure vapor infusion yields S/C composites with >50% sulfurincorporation and electrochemical performance comparable to S/C hollowshape sphere particles.

The same approach used for creating S/C composites should be applicableto other, more widely available carbon materials (e.g. coal).Specifically, if coal (ideally a high-sulfur variety) contains at least5% by weight graphitic carbon after thermal treatment, electrochemicaland/or mechanical grinding can be employed to create high surface areananosized carbon particles compatible with the foregoing templateprocessing. Using the elevated pressure vapor infusion method it ispossible to create S/C composites with comparable energy density andelectrochemical cycling stability as the hollow carbon shape materialsdescribed above.

II. Sulfur Containing Nanoparticles Comprising Vulcanized PolymultienePolymer Materials and Ion Conducting Polymer Materials

The second embodiment also describes a novel material for capturing andsequestering sulfur at a cathode within a lithium ion battery. The basicconfiguration of such a material is a silica (or other metal oxide)particle at a core linked by many polybutadiene (PBD) (i.e., moregenerally polymultiene polymer material) polyethyleneglycol (PEG) (i.e.,more generally ion conducting polymer material) diblock copolymerstrands. The PBD is cross linked with sulfur and the flowing polymerstrands that are tethered to the silica (or other metal oxide) particlehelp the capture of sulfur. As PBD is known to have a very lowconductivity, PEG which has a much higher conductivity is linked to thePBD, creating a diblock copolymer shell around the silica particle. Theconfiguration described is that of a NOHMS (nanoparticle organic hybridmaterial system). NOHMS is a novel material configuration that attachesorganic polymer dendrites to a core material such as silica. The corematerial can simply function as an anchor to form a dendrite shell layeraround it or can also provide a specific property of its own. Themulticomponent hybrid material brings about a synergistic effect bycombining the properties of several components in the nanoscale. Forthis second embodiment, the foregoing NOHMS configuration has enhancedthe capture of sulfur from leaving the area near the cathode as thedendrites function in making diffusion rather difficult.

As illustrated in FIG. 15, a synthetic scheme shows an overall processemployed in fabricating Silica/PBD/Sulfur/PEG nanoparticles inaccordance with the second embodiment. First, amine functionalizedsilica nanoparticles were synthesized by utilizing a modified Stoberprocess. To functionalize the silica outer layer with amine groups,3-trimethoxysilypropyl-diethylenetriamine was used. Also in order tolessen the aggregation of the silica particles polyethylene glycolmethyl ether was used with the silane. To control the size of thenanoparticles, different amounts of ammonium hydroxide were used. Then,the amine functionalized silica particles were used as an anchor toattach dicarboxy terminated polybutadiene strands. The monofunctionalized polyethyleneglycol was then attached to the free carboxyterminal. The process was performed using N,N-dimethylformamide as thesolvent. Alternative synthetic schemes are also considered that mayreverse ordering of the alternate levels of functionality and the orderof bonding of the PBD and PEG materials to a core metal oxide material.As well, and as needed, particular types of chemical functionality ofPBD and PEG materials may be adjusted and selected accordingly

FIG. 16 shows a titration curve for the amine group functionalizedsilica particles. The equivalence point indicates that the aminefunctionality is 5.33×10⁻⁷ moles/mg of silica particle. The amine groupsare from the silane and they surround the outer core of the silicaparticles. The amine functionalized outer layer was fabricated insteadof a hydroxyl outer layer created by the non-modified Stober processsince the dicarboxy polybutadiene will bond better with amine groups.

Size distribution measurements of the silica particles indicated anaverage size of 49.9 nanometers, a number PSD of 31.3 nanometers, anintensity PSD of 62.4 nanometers and a PDI of 0.204. The zeta potentialwas −16.5 mV with a standard deviation of 18.8 mV, a conductivity of0.447 ms/cm, an effective voltage of 147.6 volts and a count rate of45.3 kcps, showing that the particles would not aggregate and as thezeta potential for pure silica particles is −31 mV, one can see that thesurface configuration has changed. Although the standard deviationshowed that some of the particles would have a positive zeta potential,NaOH was added during the synthesis to minimize aggregation. Inaddition, NaOH had another purpose of reducing the hydrogen bondinginteraction between the silica particles and the methanol solvent, whichcaused gel formation.

The particle size data from the zetasizer was verified using TEM. FIG.17 shows the TEM image of the amine functionalized silica nanoparticles.FIG. 17 shows that most of the particles were between 15-45 nm. It wasdifficult to find particles with diameters greater than 60 nm. Duringthe synthesis the amount of ammonium hydroxide added was generallydeterminative to achieving a particular size of the silica particles.Addition of 2 ml NH4OH:3 ml TEOS resulted in a particle size of 5-10 nmwhile 3 ml NH4OH:3 ml TEOS resulted in a particle size of 60-70 nm. Theparticle size of approximately 30 nm was chosen in order to haveparticles with enough amine functionality per particle in order toachieve fluidic behavior of silica NOHMS particles while keeping thesilica fraction small.

The TGA graphs in FIG. 18 show the composition of the polymer linkedsilica nanocomposite particles. In FIG. 18a there are three peaks forthe compound. The first peak is physisorbed water and DMF that was usedas the solvent during the synthesis.

Even though the solvent was driven off by an extensive drying process(48 hours in the oven at 70 C and 24 hours in freeze drier), all thewater and DMF was not driven off. However, the temperature could not beincreased further because the PBD may crosslink at higher temperatures.The second peak is that of the silane that surrounds the silicaparticle. A TGA of the silica particle alone showed a peak around 400 Cindicating the silane decomposition temperature. The third compound thatis thermally desorbed is the PBD and the compound left after 550 C isthe silica core particle.

FIG. 18b is the TGA graph after linking PEG600 to the silica-PBDnanocomposite particle. The PEG600 polymer has a decompositiontemperature that overlaps with that of silane. So the second peakindicates both silane and PEG600. Since the relative ratio betweensilica and silane is known, one may deduce the amount of PEG600 in thenanocomposite. The ratio of PBD to PEG600 was approximately 7 to 1 whichis the ratio between their molecular weights. This may indicate that thePEG600 is well distributed and that the PBD and PEG particles arelinked.

FIG. 18c is the TGA graph after linking PEG2000 to the silica-PBDnanocomposite particle. The PEG2000 had a decomposition temperature thatoverlapped with the silane but its intensity was much greater. ThePEG2000 amount was also calculated by deducting the amount of silanefrom the second peak. Even though the molecular weight of PEG2000 islower than that of PBD, the weight fraction is similar. An additionalcentrifugation step may decrease the PEG2000 content.

FIG. 19 shows the rheological data of the NOHMS particles and wasmeasured using a flat 9.958 mm diameter plate while varying the strainamplitude at constant w. The temperature was set to 100 C. The gapbetween the plates was 0.11 mm for the PEG600 nanocomposite and 0.18 mmfor the PEG2000 nanocomposite.

Rheology data was collected to determine the class of the particlecreated. From FIG. 19, one may conclude that both particles are in thegroup of soft glasses. It was identified that the pronounced peak of theloss modulus after the fall of the storage modulus is a robust featureof soft glassy materials. This peak shows the material's transition froma solid to liquid-like behavior. Especially, the crossover of thestorage modulus and loss modulus shows that the liquid-like behavior ofthe nanocomposite takes over the solid-like behavior. The polymerstrands that form the outer lining of the silica particles intertwinewith those of neighboring silica particles. As more strain is impartedto the particles, the loss modulus rises indicating energy dissipationand when the polymers break free of one another the loss modulus drops.The energy required to achieve the loss modulus peak and the fall in thestorage modulus are at similar strains. The flat storage modulus is acharacteristic of elastic polymers and its fall indicates that theparticles are transitioning to a more freely flowing particle. From FIG.19 one may also see that the shorter PEG polymer shows the peak at lowerstrain and this may be caused by shorter chain lengths.

FIG. 20 shows the DSC graphs for the Silica-PBD-PEG600 andSilica-PBD-PEG2000 nanocomposites. Silica-PBD-PEG600 nanocomposite had aTg at −80.44 C for the PBD. In comparison, silica-PBD-PEG2000nanocomposite had two Tg which were at −81.24 C and −63.80 C. The firstTg was for the PBD which has a Tg of −77 C on its own. The second Tg wasfor the PEG2000. The Tg for the PEG600 was difficult to observe in thedata. Also the PEG2000 nanocomposite had a Tc at −38.49 C but the PEG600nanocomposite did not show any Tc. The Tm for the PEG600 was at 9.75 Cwhile that of PEG 2000 was at 3.16 C. Usually higher molecular weightpolymers have higher melting points but the data showed otherwise. Tm ofPEG2000 alone is approximately at 60 C. This is probably due to theinteraction of the PEG2000 with the PBD.

FIG. 21 shows the cyclic performance of Li/S batteries fabricated usingthe NOHMS composites described above. The results show that compared tothe sulfur cathode battery which was used as a control, the NOHMSbatteries show substantially higher cyclic performances in terms oflimited capacity loss as a function of cycling.

Cathode material compositions for the batteries evaluated in FIG. 21 areshown in Table 1, as follows,

TABLE 1 Cathode Vulcanized Sulfur Sulfur NOHMS 600 NOHMS 2000 WeightComposition Compound (%) (phr) (%) (phr) (%) (phr) (%) Sulfur 60% 12.05.8% 6.8 3.6% 4.6 2.5% Carbon B 20% 41.7 20.0% 38.1 20.0% 36.6 20.0%PVDF-HFP 20% 41.7 20.0% 38.1 20.0% 36.6 20.0% Tetraethylthiuramdisulfide 0% 2.0 1.0% 1.1 0.6% 0.8 0.4% ZnO 0% 8.0 3.8% 4.5 2.4% 3.11.7% Stearic Acid 0% 3.2 1.5% 1.8 1.0% 1.2 0.7% PEG + Silane + Silica 0%0.0 0.0% 43.2 22.7% 61.7 33.8% PBD 0% 100.0 47.9% 56.8 29.8% 38.3 21.0%

In the performed experiment within the context of FIG. 21, the sulfurcontent varied for different types of batteries. This is because thesulfur content was kept at 12 per hundred rubber (phr), in which therubber only indicates the weight of the PBD. As the % weight content ofPBD changed, that of sulfur changed as well for each type of battery.

Experimental Details

For synthesizing amine functionalized silica particles, 3 ml oftetraethyl orthosilicate (Aldrich), 60 ml of methanol (Aldrich), and 2.5ml of ammonium hydroxide (EMD) were mixed and left to stir for 30minutes. Then 2.5 ml of 3-trimethoxysilylpropyl-diethylenetriamine(Silane) (Gelest), 2.5 grams of polyethylene glycol methyl ether (mPEG)(Aldrich), and 20 ml of methanol was added to the original mixture.After an additional five minutes, 2 ml of 0.6M NaOH solution was added.This mixture was left to react for an additional 12 hours.

A Nano Zetasizer apparatus (Nano-ZS Malvern Co.) was used to measure thesize and zeta potential of the silica particles. The measurements wereperformed using methanol (Visc=0.5476, RI=1.326) as the solvent, andsilica (Abs=0.10, RI=1.500) as the particle. To measure the aminefunctionality of the particles, 20 ml of the silica solution was mixedwith 20 ml of DI water and left in a 70 C oven until the methanol andammonia solution evaporated. Titration using a pH meter was performed toobtain the equivalence point. The sodium hydroxide that was still in thesample was accounted for in the titration calculation. TEM (FEI Tecnai12 Spirit Twin) analysis was used to verify the size and presence ofsilica particles in the solution.

For polybutadiene linkage to silica, first, a hot plate was used at 150C to heat and stir 100 ml of N,N-dimethylformamide (DMF) (Aldrich). 50ml of the methanol solution with silica particles was slowly added tothe DMF. The mixture was stirred for an hour to remove the methanol andammonia. 12.5 grams of dicarboxy terminated polybutadiene (PBD) (Mn=4200Aldrich) and 50 ml of tetrahydrofuran (THF) (JT Baker) was mixed andstirred until the polymer completely dissolved. The amount of thepolymer was chosen so that there would be 4 times molar excess of thecarboxylic groups of the PBD compared to the amine groups on the silane.The volume of the silica DMF solution was set to 50 ml by adding moreDMF to the solution. The PBD THF solution and silica DMF solution wasmixed by slowly adding the silica DMF solution. The reaction was left tocontinue for 24 hours. Centrifugation (AccuSpin 400 Fisher Scientific)was used to separate out the silica-PBD particles. The free PBDincluding supernatant was discarded and the precipitates were collected.Additional centrifugation was performed in a solution of 4:3 volumeratio of THF and DMF. This ratio was chosen since PBD started toprecipitate when equal volume amounts of THF and DMF were used.

For polyethylene glycol linkage to the silica-polybutadiene, PEG wasadded in a 2 (PEG) to 3 (carboxylic group) ratio. Two separate batchesof the sample were made and into each, PEG with two different molecularweights was added. They wereO-(2-aminopropyl)-O′-(2-methoxyethyl)polypropylene glycol (PEG600)(Mn=600 Aldrich), and polyetheramine (PEG2000) (Jeffamine M-2070,Mn=2000, Huntsman). The mixture was left to mix for 24 hours and thenleft to dry at 70 C.

Vulcanization was performed at 150 C. For the accelerator, 2 phr oftetraethylthiuram disulfide (Acros Organics) was used. For theactivator, 8 phr of zinc oxide (Aldrich Co.) was used. Also 3.2 phr ofstearic acid (97%, Fluka Co.) and 12 phr of sulfur (Reagent grade, 100mesh, Aldrich Co.) was used. For the NOHMS particles the fraction of PBDin the composite was used in calculating relative amounts of reactantsfor the vulcanization process as only the PBD would crosslink with thesulfur.

To grind the rubber material that was used as a control, liquid nitrogenand dry ice was used to make the rubber brittle and then was ground intopowder. Carbon black (Super P-Li, TIMCAL Co.) was used as theconductivity aid, PVDF-HFP (Kynar 2801, Arkema Inc.) was used as thebinder, and DMF (Aldrich) was used as the solvent. The NOHMS material,carbon black, and PVDF-HFP was mixed in 60:20:20 weight ratio. Theslurry was left to mix for 24 hours and then placed on a copper disk. Itwas dried in an oven at 70 C for 4 hours and at 120 C under vacuum for12 hours. Control samples were fabricated which included: (1) sulfur,and (2) 12 phr of sulfur vulcanized PBD as the active material. Thecells with NOHMs as the active material also had 12 phr of sulfur. Thecells were made with lithium (0.75 mm thick, 99.9%, Sigma Aldrich) atthe anode. The electrolyte was 0.5M solution of lithium bis(trifluoromethane) sulfonimide (Aldrich), in a 50:50 weight ratiomixture of 1,3-dioxolane (Aldrich) and dimethoxyethane (Aldrich).

All references, including publications, patent applications, and patentscited herein are hereby incorporated by reference in their entireties tothe extent allowable and to the same extent as if each reference wasindividually and specifically indicated to be incorporated by referenceand was set forth in its entirety herein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) is to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. The term “connected” is to beconstrued as partly or wholly contained within, attached to, or joinedtogether, even if there is something intervening.

The recitation of ranges of values herein is merely intended to serve asa shorthand method of referring individually to each separate valuefalling within the range, unless otherwise indicated herein, and eachseparate value is incorporated into the specification as if it wasindividually recited herein.

All methods described herein can be performed in any suitable orderunless otherwise indicated herein or otherwise clearly contradicted bycontext. The use of any and all examples, or exemplary language (e.g.,“such as”) provided herein, is intended merely to better illuminateembodiments of the invention and does not impose a limitation on thescope of the invention unless otherwise claimed.

No language in the specification should be construed as indicating anynon-claimed element as essential to the practice of the invention.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the embodiments withoutdeparting from the spirit and scope of the invention. There is nointention to limit the invention to the specific form or formsdisclosed, but on the contrary, the intention is to cover allmodifications, alternative constructions, and equivalents falling withinthe spirit and scope of the invention, as defined in the appendedclaims. Thus, it is intended that the present invention cover themodifications and variations of this invention provided they come withinthe scope of the appended claims and their equivalents.

Therefore, the embodiments are illustrative of the invention rather thanlimiting of the invention. Revisions and modifications may be made tomethods, materials, structures and dimensions of a nanoporous material,nanoparticle and a method for fabricating the nanoporous materials ornanoparticle in accordance with the embodiments while still providing ananoporous material, a nanoparticle or a method for fabricating thenanoporous material or the nanoparticle in accordance with theinvention, further in accordance with the accompanying claims.

What is claimed is:
 1. A material comprising at least one nanoparticlecomprising: a carbon material support comprising a hollow sphere shapemesoporous carbon material; and an elemental sulfur material supportedon and within the carbon material support, wherein the material is anactive material.
 2. The material of claim 1 wherein: a cyclicvoltammogram of a lithium-sulfur cell that includes the material withina cathode shows a stable reduction peak at about 2.4 volts over at least10 cyclic voltammogram cycles; the cyclic voltammogram uses a lithiumbis (trifluoromethane sulfone) imide in tetraglyme electrolyte; thecyclic voltammogram also shows a stable reduction peak at about 2.0volts; and the cyclic voltammogram also shows a stable oxidation peak atabout 2.35 volts and a stable oxidation peak at about 2.45 volts.
 3. Thematerial of claim 2 wherein the cyclic voltammogram shows a stablereduction peak at about 2.4 volts over at least 60 cyclic voltammogramcycles.
 4. The material of claim 2 wherein the cyclic voltammogram showsa stable reduction peak at about 2.4 volts over at least 100 cyclicvoltammogram cycles.
 5. The material of claim 1 wherein the carbonmaterial support comprises at least in-part a graphite carbon material.6. The material of claim 1 wherein the elemental sulfur materialcomprises an amorphous sulfur material comprising up to about 70 percentby weight sulfur material.
 7. The material of claim 1 wherein a cyclicvoltammogram of a lithium-sulfur cell that includes the nanoparticlewithin a cathode shows a stable reduction peak at about 2.4 volts. 8.The material of claim 1 wherein a cyclic voltammogram of alithium-sulfur cell that includes the active material within a cathodecomprising a stable reduction peak of at least about 2.0 volts.
 9. Anelectrode comprising: a conductive support; and a coating located uponthe conductive support, the coating comprising an material comprising ananoparticle comprising: a carbon material support comprising a hollowsphere shape mesoporous carbon material; and an elemental sulfurmaterial supported on and within the carbon material support.
 10. Theelectrode of claim 9 wherein a cyclic voltammogram of a lithium-sulfurcell that includes the material within the electrode shows a stablereduction peak at about 2.4 volts over at least 60 cyclic voltammogramcycles.
 11. The electrode of claim 10 wherein the cyclic voltammogram ofthe electrode shows a stable reduction peak at about 2.4 volts over atleast 100 cyclic voltammogram cycles.
 12. The electrode of claim 9wherein a cyclic voltammogram of a lithium-sulfur cell that includes theactive material within a cathode shows a stable reduction peak at about2.4 volts.
 13. The electrode of claim 9 wherein a cyclic voltammogram ofa lithium-sulfur cell that includes the active material within a cathodecomprising a stable reduction peak of at least about 2.0 volts.
 14. Abattery comprising an electrode comprising: a conductive support; and acoating located upon the conductive support, the coating comprising anmaterial comprising a nanoparticle comprising: a carbon material supportcomprising a hollow sphere shape mesoporous carbon material; and anelemental sulfur material supported on the carbon material support. 15.The battery of claim 14 wherein: the electrode comprises a cathode; andthe battery comprises a lithium ion battery.
 16. The battery of claim 14wherein a cyclic voltammogram of a lithium-sulfur cell that includes theactive material within the electrode shows a stable reduction peak atabout 2.4 volts over at least 60 cyclic voltammogram cycles.
 17. Thebattery of claim 16 wherein the cyclic voltammogram of the battery showsa stable reduction peak at about 2.4 volts over at least 100 cyclicvoltammogram cycles.
 18. The battery of claim 14 wherein a cyclicvoltammogram of a lithium-sulfur cell that includes the active materialwithin a cathode shows a stable reduction peak at about 2.4 volts. 19.The battery of claim 14 wherein a cyclic voltammogram of alithium-sulfur cell that includes the active material within a cathodecomprising a stable reduction peak of at least about 2.0 volts.
 20. Anactive material comprising at least one nanoparticle consistingessentially of: a carbon material support consisting essentially of ahollow shaped sphere mesoporous carbon material; and an elemental sulfurmaterial supported on and within the carbon material support.
 21. Theactive material of claim 20 wherein a cyclic voltammogram of alithium-sulfur cell that includes the nanoparticle within a cathodeshows a stable reduction peak at about 2.4 volts.